U.S. patent application number 10/347681 was filed with the patent office on 2003-07-17 for deuterated semi-conducting organic compounds used for opto-electronic devices.
This patent application is currently assigned to Canon Kabushiki Kaisha. Invention is credited to Li, Xiao-Chang Charles, Ueno, Kazunori.
Application Number | 20030134140 10/347681 |
Document ID | / |
Family ID | 24943793 |
Filed Date | 2003-07-17 |
United States Patent
Application |
20030134140 |
Kind Code |
A1 |
Li, Xiao-Chang Charles ; et
al. |
July 17, 2003 |
Deuterated semi-conducting organic compounds used for
opto-electronic devices
Abstract
Organic semiconductors consisting of conjugated chromophores
wherein one or more hydrogen atoms are deuterated are disclosed.
Methods of preparing such organic semiconductors are described. The
organic semiconducting compounds exhibit remarkably high
luminescence and good thermal stability. Applications of these
materials for optoelectronic devices, such as light-emitting
devices and photodiodes, with enhanced performance and lifetime are
disclosed. The disclosed materials can be used as emissive layer,
charge-transporting layer, or energy transfer (i.e. phosphorescence
dopant) material in organic light-emitting devices.
Inventors: |
Li, Xiao-Chang Charles;
(Union City, CA) ; Ueno, Kazunori; (Kanagawa,
JP) |
Correspondence
Address: |
FITZPATRICK CELLA HARPER & SCINTO
30 ROCKEFELLER PLAZA
NEW YORK
NY
10112
US
|
Assignee: |
Canon Kabushiki Kaisha
|
Family ID: |
24943793 |
Appl. No.: |
10/347681 |
Filed: |
January 22, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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10347681 |
Jan 22, 2003 |
|
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09732511 |
Dec 7, 2000 |
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Current U.S.
Class: |
428/621 ;
428/690 |
Current CPC
Class: |
H01L 51/0077 20130101;
H01L 51/0083 20130101; H01L 51/5012 20130101; H01L 51/0071
20130101; H01L 51/0078 20130101; H01L 51/0085 20130101; Y10T
428/12535 20150115; H01L 51/0039 20130101; H01L 51/0081 20130101;
H01L 51/0035 20130101; Y10S 428/917 20130101; H01L 51/006 20130101;
H01L 51/0036 20130101; H01L 51/008 20130101; H01L 51/004 20130101;
H01L 51/0054 20130101; H01L 51/0058 20130101; H01L 51/0089
20130101; H01L 51/0038 20130101; H01L 51/0059 20130101 |
Class at
Publication: |
428/621 ;
428/690 |
International
Class: |
B21D 039/00 |
Claims
1. An organic semiconductor comprising a conjugated chromophore
selected from a linear conjugated organic compound or a polymer, a
cyclic ring, a fused cyclic ring, a heterocyclic ring, a fused
heterocyclic ring, a chelate or oraganometalic material having the
formula C.sub.AM.sub.B, where C denotes a conjugated chromophore, M
denotes a metal selected from, Li, Na, K, Be, Mg, Ca, Ti, Cr, Mo,
Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Zn, Cd, B, Al, Ga, In,
Si, N, P, and A and B denote a number from 1 to 10, respectively,
and combinations thereof, said chromophore having with at least 5
conjugated bonds wherein protons linked to the conjugated bonds are
partially or fully deuterated.
2. An organic semiconductor according to claim 1, wherein the
conjugated chromophore is partially deuterated, and wherein
un-deuterated sites are chemically bound to a moiety selected from
hydrogen atoms, halogen atoms, alkyl, alkoxyl, thiol, silyl,
aromatic rings, or heteroaromatic rings.
3. An organic semiconductor according to claim 1, wherein the
organic semiconductor is luminescent.
4. An organic semiconductor according to claim 1, wherein the
organic semiconductor possesses charge injection, hole blocking, or
exciton blocking properties.
5. An organic semiconductor according to claim 1, wherein the
organic semiconductor promotes energy transfer.
6. An organic semiconductor according to claim 1, wherein the
organic semiconductor produces greater than 25% singlet excitons
for light emission.
7. An organic semiconductor comprising a conjugated chromophore
with a linear conjugated organic compound or a polymer with at
least 5 conjugated bonds, wherein protons linked to the conjugated
bonds are partially or fully deuterated.
8. An organic semiconductor according to claim 7, wherein the
conjugated chromophore is partially deuterated, and wherein
un-deuterated sites are chemically bound to a moiety selected from
hydrogen atoms, halogen atoms, alkyl, alkoxyl, thiol, silyl,
aromatic rings, or heteroaromatic rings.
9. An organic semiconductor according to claim 7, wherein the
organic semiconductor is luminescent.
10. An organic semiconductor according to claim 7, wherein the
organic semiconductor possesses charge injection, hole blocking, or
exciton blocking properties.
11. An organic semiconductor according to claim 7, wherein the
organic semiconductor promotes energy transfer.
12. An organic semiconductor according to claim 7, wherein the
organic semiconductor produces greater than 25% singlet excitons
for light emission.
13. An organic semiconductor comprising a conjugated chromophore
with a cyclic ring, a fused cyclic ring, or a combination thereof,
in the form of a conjugated organic compound or a polymer with at
least 5 conjugated bonds, wherein protons linked to the conjugated
bonds are partially or fully deuterated.
14. An organic semiconductor according to claim 13, wherein the
conjugated chromophore is partially deuterated, and wherein
un-deuterated sites are chemically bound to a moiety selected from
hydrogen atoms, halogen atoms, alkyl, alkoxyl, thiol, silyl,
aromatic rings, or heteroaromatic rings.
15. An organic semiconductor according to claim 13, wherein the
organic semiconductor is luminescent.
16. An organic semiconductor according to claim 13, wherein the
organic semiconductor possesses charge injection, hole blocking, or
exciton blocking properties.
17. An organic semiconductor according to claim 13, wherein the
organic semiconductor promotes energy transfer.
18. An organic semiconductor according to claim 13, wherein the
organic semiconductor produces greater than 25% singlet excitons
for light emission.
19. An organic semiconductor of the formula C.sub.AM.sub.B, where C
denotes a conjugated chromophore, wherein protons linked to the
conjugated bonds are partially or fully deuterated; M denotes a
metal selected from, Li, Na, K, Be, Mg, Ca, Ti, Cr, Mo, Mn, Fe, Ru,
Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Zn, Cd, B, Al, Ga, In, Si, N, and
P; A and B denote a number from 1 to 10, respectively.
20. An organic semiconductor according to claim 19, wherein A and B
denote a number from 1 to 4, respectively.
21. An organic semiconductor according to claim 19, wherein the
conjugated chromophore is partially deuterated, and wherein
un-deuterated sites are chemically bound to a moiety selected from
hydrogen atoms, halogen atoms, alkyl, alkoxyl, thiol, silyl,
aromatic rings, or heteroaromatic rings.
22. An organic semiconductor according to claim 19, wherein the
organic semiconductor is luminescent.
23. An organic semiconductor according to claim 19, wherein the
organic semiconductor possesses charge injection, hole blocking, or
exciton blocking properties.
24. An organic semiconductor according to claim 19, wherein the
organic semiconductor promotes energy transfer.
25. An organic semiconductor according to claim 19, wherein the
organic semiconductor produces greater than 25% singlet excitons
for light emission.
26. An organic semiconductor according to claim 1, fabricated as an
organic luminescent device.
27. An organic semiconductor according to claim 7, fabricated as an
organic luminescent device.
28. An organic semiconductor according to claim 13, fabricated as
an organic luminescent device.
29. An organic semiconductor according to claim 19, fabricated as
an organic luminescent device.
30. An organic luminescent device comprising: a first electrode
surface; a first thin film of conjugated luminescent polymer
comprising an organic semiconductor according to claim 1, wherein
the luminescent polymer is electrically coupled to the first
electrode surface; and a second electrode, electrically coupled to
the conjugated luminescent polymer.
Description
TECHNICAL FIELD
[0001] The present invention relates to new semiconducting organic
compounds and/or polymers for use in optoelectronic devices that
contain completely or partially deuterated conjugated backbones,
which can promote luminescence and thermal stability of the
materials. More particularly, the present invention relates to the
effective modification of the molecular structure of known
luminescent materials with conjugated backbones containing hydrogen
atoms by replacing one or more of the hydrogen atoms with deuterium
atoms. The resulting deuterated material is significantly altered
and has greatly improved performance over known luminescent
light-emitting materials.
BACKGROUND OF THE INVENTION
[0002] Organic semiconductors have the benefit of low cost
processing, easy control of properties by changing chemical
structures, and attractive electronic properties. These materials
are usually composed of conjugated chromophores linked by saturated
or unsaturated linkage units. Many interesting applications have
been explored in recent years, such as organic light-emitting
devices [C. W. Tang, S. A. Van Slyke, Appl. Phys. Lett., 1987,
51(12), 913; J. H. Burroughes; D. D. C. Bradley; A. R. Brown; R. N.
Marks; K. Mackay; R. H. Friend; P. L. Bum and A. B. Holmes, Nature
1990, 347, 539. R. H. Friend; R. W. Gymer; A. B. Holmes; J. H.
Burroughes; R. N. Marks; C. Taliani; D. D. C. Bradley; D. A.
Dossantos; J. L. Bredas; M. Logdlund and W. R. Salaneck, Nature
1999, 397, 121.], organic lasers [F. Hide; M. A. Diaz-Garcia; B. J.
Schwartz and A. J. Heeger, Acc. Chem. Res. 1997, 30, 430.], organic
thin-film transistors [F. Gamier, R. Hajlaoui, A. Yassar, P.
Srivastava, Science, 1994, 265, 1684], and organic photodiodes.
[0003] One application of organic semiconductors is as an active
flat-panel display or organic light-emitting device (OLED). Such
devices offer many unique features, including a low cost, full
color, active display with the possibility of a thinner, lighter,
larger and more flexible display module, with wider viewing angles
(>160.degree.), compared to conventional flat-panel display
devices. All these features imply a strong competitive alternative
to replace present LCD displays. Such devices consist of one or
several semiconducting organic layer(s) sandwiched between two
electrodes. When an electric field is applied, electrons are
injected by the cathode into the lowest un-occupied molecular
orbital (LUMO) of the adjacent molecules, and holes are injected by
the anode into the highest occupied molecular orbital (HOMO). As a
result of recombination of electrons and holes, an excited state,
called singlet exciton, is formed which returns back to the ground
state upon emission of light corresponding to the energy band gap
of the emissive material. The selection of emissive materials not
only can influence the emission color, but also the light emission
efficiency (photons per injected electron) and the light emission
brightness and lifetime. In practical display applications, color
purity, light-emission efficiency, brightness and lifetime are
important parameters.
[0004] There have been various organic semiconductor materials
developed in the past a few years [Y. Sato, Semiconductors &
Semimetals, 2000, 64, 209; A. Kraft; A. C. Grimsdale and A. B.
Holmes, Angew. Chem.--Int. Ed. In Engl. 1998, 37, 402; Li, X. -C.,
Moratti, S. C.; In Photonic Polymer Systems: Fundamentals, Methods,
and Applications; Wise, D. L.; Wnek, G. E.; Trantolo, D. J. ;
Cooper, T. M.; Gresser, J. D.; Eds.; Marcel Dekker, Inc.: New York,
Chapter 10, 1998, p. 335]. Many prototypes of OLED display modules
have been demonstrated with the use of organic luminescent
compounds (small molecular compounds or polymers). However, only
limited commercial products of OLEDs have been launched, due both
to the difficulty of technological integration and to the overall
performance of the present organic semiconducting materials, which
include emissive materials and charge transporting materials.
Accordingly, there is a need in the art to develop new materials
that exhibit combinatory high performance of luminescence,
excellent stability, and good lifetime.
[0005] The search for new organic materials used for optoelectronic
devices, such as organic light-emitting devices, has been a very
active field in recent years. This includes research relating to
organic semiconductors and organic polymeric materials that present
strong luminescence and good processibility. Most researchers have
focused on varying the structure of either the core chromophore
and/or polymer backbone, and on modifying linkages for solubility,
for charge injection ability, or for other processing
functionality. These methods require innovative molecular design,
coupled with skillful chemical synthesis, which are time consuming
and expensive in order to screen off undesired products.
[0006] It is an object of the present invention to provide a unique
and effective manner to chemically modify known and novel
optoelectronic materials by replacing protons with deuterium atoms
on the conjugated chromophores. It is another object of the
invention to provide a method to design and synthesize new
luminescent organic materials containing deuterium atoms for their
application in optoelectronic devices, such as light-emitting
devices. It is further another object of the invention to improve
OLED performance with brighter luminance and better thermal
stability.
SUMMARY OF THE INVENTION
[0007] The present invention relates to deuterated semiconductor
organic compounds used in optoelectronic devices and to processes
of preparing such deuterated compounds. In one process within the
scope of the present invention, known and novel organic
semiconductor compounds are deuterated by replacing one or more
hydrogen atoms covalently bonded to carbon atoms with deuterium
atoms.
[0008] Deuterium is a non-radiative isotope of hydrogen, which is
sometimes called heavy hydrogen due to its doubled atomic mass. The
difference between hydrogen and deuterium has fairly small chemical
effects; however, there are important physical effects because of
the mass difference between the isotopes. The heavier isotope,
deuterium, lies lower in the potential well, and hence has a lower
zero-point energy and vibration frequency, and smaller vibration
amplitude than hydrogen. Because of the asymmetry of the potential
well, bond lengths and bond angles involving deuterium are
different than those involving hydrogen. The observed smaller
amplitude of the C-D stretching and bending motion, relative to
C--H, should be best accounted for with a smaller van der Waals
radius for D than for H. The weak vibronic coupling in the
deuterated system has been used to theoretically predict higher
fluorescence quantum yield [A. L. Burin and M. A. Ratner, J. Chem.
Phys., 1998, 109, 6092]. Spectroscopic studies indicate that
deuterated phenanthrene has a smaller non-radiative triplet rate
constant than its aromatic molecule [S. M. Ramasamy, R. J.
Hurtubise, Appl. Spectroscopy, 1996, 50(9), 1140].
[0009] Deuterium is also found to act as an apparent
electron-donating inductive substituent relative to hydrogen. The
isotope effects may be applied in the design of new luminescent
materials with enhanced charge-injection ability. Additionally, it
is know that the C-D bond is shorter than the C--H as a result of
the anharmonicity of the bond stretching potential. [M. L. Allinger
and H. L. Flanagan, J. Computational Chem. 1983, 4(3), 399]. This
means the carbon-deuterium chemical bond is stronger, more stable,
and reacts more slowly than the carbon-hydrogen chemical bond, so
that the deuterated organic system has better thermal stability,
and longer lifetime in optoelectronic devices. Deuterated
luminescent material may also have a higher electroluminescent
quantum yield as a result of smaller non-radiative triplet
rate.
[0010] In the prior art, deuterated hydrocarbon lubricants have
better anti-oxidation and improved stability than normal
hydrocarbon lubricants [U.S. Pat. No. 4,134,843]. A deuterated
polymer has been used for optical fiber with low attenuation
optical loss [U.S. Pat. No. RE031,868]. Deuterated pharmaceuticals
or drugs can enhance drug's efficacy and activity. [U.S. Pat. No.
4,898,855 and U.S. Pat. No. 5,846,514]. Deuterium-treated
semiconductor devices have been disclosed [U.S. Pat. No.
5,872,387], wherein degradation of inorganic semiconductor devices
has been reduced by using deuterium passivation; deuterium
incorporation at the SiO.sub.2/Si interface has been reported to
improve the hot carrier reliability of CMOS transistors. [J. Lee,
K. Cheng, et al, IEEE Electron Device Letters, 2000, 21(5), 221].
Compared with normal hydrogen treated device, the deuterium treated
device has a significant lifetime improvement (90 times).
[0011] The deuterated organic semiconductor materials within the
scope of the present invention are preferably luminescent.
Luminescence here means either fluorescence (singlet emission) or
phosphorescence (triplet emission). The deuterated organic
semiconductor materials may possess charge injection (electron
injection or hole injection), hole blocking, or exciton blocking
properties. As used herein, hole blocking property means that the
semiconductor material allows electrons to transport, but not
holes. Whenever a material has a low mobility for hole transporting
(less than 10.sup.-6 cm/V.multidot.s), or a very high HOMO (highest
occupied molecular orbital) level, the material normally possesses
hole blocking properties. As used herein, exciton blocking property
means that excitons are confined within an emissive layer by using
another material layer which does not readily transport excitons
(usually non-emissive layer).
[0012] The deuterated organic semiconducting material preferably
possesses a strong energy transfer property. As used herein, energy
transfer includes a Forster process where a higher energy singlet
transfers to a lower energy singlet. An example is a blue emissive
polymer (host) doped with red emissive material (guest) [like
tetraphenylporphyrin doped polyfluorene reported by T. Virgili, et
al., Adv. Mater., 2000, 12(1), 58]. The doping level is usually
from 0.1-15%, but more than 90% energy will transfer into the red
emissive material, thus lead to red emission rather than blue
emission. As used herein, energy transfer also includes an
intersystem transfer where the singlet energy transfers to a
triplet, and thus lead to phosphorescence. An example is a yellow
emissive polymer doped with rare earth metal complexes to lead to
electrophosphorescence [M. D. McGehee, et al., Adv. Mater., 1999,
11(16), 1349; Appl. Phys. Lett., 1999, 75, 4]. This
triplet-emission can potentially lead to very high quantum
efficiency because the maximal probability of a triplet is 75%.
[0013] The deuterated organic semiconducting materials preferably
produce more singlet energy states for light-emission, compared to
non-deuterated materials. For most organic fluorescent materials,
the maximum singlet production probability under electrical
excitation is about 25%. Deuterated materials may exceed that limit
for electrofluorescence because of their slow triplet production
rate. Therefore, deuterated materials may efficiently produce more
singlets than non-deuterated materials, with a potential singlet
production exceeding 25%.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 is a cross-section illustration of a typical single
layer light emitting device.
[0015] FIG. 2 is a cross-section illustration of a typical triple
layer light emitting device.
[0016] FIG. 3 is a graph of the UV spectrum of the sulfonium
polymer precursor and the converted conjugated polymer deuterated
PPV (D-PPV), showing the band gap changes from 3.42 eV to 2.45
eV.
[0017] FIG. 4 is a graph of the ultraviolet (UV) and visible
photoluminescent spectrum of the deuterated polymer D-PPV.
[0018] FIG. 5 is a graph of the ultraviolet (UV) spectra and the
photoluminescent spectrum (excited by 400 nm UV light) of
semi-deuterated MEH-PPV.
[0019] FIG. 6 is a graph of the electroluminescence spectrum of
Ir(ppy).sub.3 in the device structure of ITO/NPD 40 nm/CBP+11%
Ir(ppy).sub.3 20 nm/BCP 10 nm/Alq3 40 nm/LiF 0.75 nm/Al.
[0020] FIG. 7 is a graph of the electroluminescent spectrum of
Ir(ppy).sub.3-d8 in the device structure of ITO/NPD 40 nm/CBP+11%
Ir(ppy).sub.3-d8 20 nm/BCP 10 nm/Alq3 40 nm/LiF 0.75 nm/Al.
[0021] FIG. 8 is a comparison graph of the relationship of external
quantum efficiency vs. current density for the device in Example 10
(square) and for the device in Example 11 (circle).
[0022] FIG. 9 is a comparison graph of the relationship of
luminance efficiency vs. current density for the device in Example
10 (square) and for the device in Example 11 (circle).
DETAILED DESCRIPTION OF THE INVENTION
[0023] Virtually all organic luminescent materials now marketed
contain hydrogen atoms, each of which has a molecular mass of one.
According to the present invention one or more of the hydrogen
atoms on a conjugated chromophore or a conjugated polymer are
deuterated. The molecular mass becomes higher, and the optical and
electronic properties of the conjugated luminescent material are
altered and improved. The deuterated organic semiconductor has
improved performance, for instance, higher fluorescence yield and
more stability than its non-deuterated analogue.
[0024] There are several deuterated structures or structural
combinations that may be used to form conjugated chromophores that
are useful for opto-electronic applications, with particularly
application in light-emitting devices.
[0025] 1. A conjugated chromophore, as used herein, includes a
linear conjugated organic compound or a polymer with at least 5
conjugated bonds, wherein protons linked to the conjugated bonds
are partially or fully deuterated. Examples of typical backbones of
conjugated chromophore compounds for this category can be described
as in Scheme 1: 1
[0026] If partially deuterated, the un-deuterated sites for the
compounds or polymers in Scheme 1 may be linked with hydrogen
atoms, halogens such as F, Cl, Br, etc; or alkyl, alkoxyl, thiol,
silyl; aromatic rings such as phenyl and naphthalene; or
heteroaromatic rings, such as thiophene, pyridine, and
quinoline.
[0027] 2. A conjugated chromophore, as used herein, also includes a
cyclic ring, fused cyclic ring, and combinations thereof, that form
a conjugated organic compound or a polymer with at least 5
conjugated bonds, wherein protons linked to the conjugated bonds
are partially or fully deuterated. Examples of typical backbones of
conjugated organic compounds for this category can be described as
in Scheme 2, below. The protons linked with aromatic rings of the
compounds in Scheme 2 should be partially or fully deuterated. If
partially deuterated, the un-deuterated sites may be linked with
hydrogen atoms, halogens such as F, Cl, Br, etc.; or alkyl,
alkoxyl, thiol, silyl; aromatic rings such as phenyl and
naphthalene; or heteroaromatic rings, such as thiophene, pyridine,
and quinoline. 23
[0028] 3. A conjugated chromophore, as used herein, also includes
heterocyclic ring, fused heterocyclic ring, and combinations
thereof, that form a conjugated organic compound or a polymer with
at least 5 conjugated bonds, wherein protons linked to the
conjugated bonds are partially or fully deuterated. Examples of
typical backbones of conjugated organic compounds for this category
can be described as in Scheme 3. The protons linked with the
heterocyclic rings of the compounds in Scheme 3 should be partially
or fully deuterated. If partially deuterated, the un-deuterated
sites may be linked with hydrogen atoms; halogens such as F, Cl,
Br, etc.; alkyl, alkoxyl, thiol, silyl; aromatic rings such as
phenyl and naphthalene; or heteroaromatic rings, such as thiophene,
pyridine, and quinoline. 4
[0029] 4. A conjugated chromophore, as used herein, also includes a
metal chelated compound or a organometallic compound with a formula
of C.sub.AM.sub.B, where C denotes a chromophore selected from
category 1, 2 or 3; and M denotes a metal selected from, Li, Na, K,
Be, Mg, Ca, Ti, Cr, Mo, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu,
Zn, Cd, B, Al, Ga, In, Si, N, P; A and B denote the number from 1
to 10, preferentially 1-4. The protons linked with the chromophore
material of the compounds in Scheme 4 should be partially or fully
deuterated. Examples of this category compounds are presented in
Scheme 4. If partially deuterated, the un-deuterated sites may be
linked with hydrogen atoms, halogens such as F, Cl, Br, etc.;
alkyl, alkoxyl, thiol, silyl; aromatic rings such as phenyl and
naphthalene; or heteroaromatic rings, such as thiophene, pyridine,
and quinoline. 56
[0030] 5. A conjugated chromophore, as used herein, also includes a
combination of the compounds disclosed in categories 1, 2, 3 and 4,
above, to form a conjugated organic compound or a polymer with at
least 5 conjugated bonds wherein protons linked to the conjugated
bonds are partially or fully deuterated. A few examples of
compounds within this category compounds are presented in Scheme 5.
If partially deuterated, the un-deuterated sites may be linked with
hydrogen atoms, halogens such as F, Cl, Br, etc.; alkyl, alkoxyl,
thiol, silyl; aromatic rings such as phenyl and naphthalene; or
heteroaromatic rings, such as thiophene, pyridine, and quinoline.
78
[0031] The present invention is also directed to organic electronic
devices containing the foregoing deuterated conjugated
semiconducting compounds and polymers. Such devices typically
include at least one thin film of the deuterated conjugated
compound or polymer coupled to a pair of electrodes. Additional
thin films of conjugated semiconducting material can be used. In
such cases, one thin film may be configured to promote electron
transport and a second thin film may be tuned to promote hole
transport. When the organic electronic device is fabricated with a
plurality of thin films of conjugated semiconducting compounds or
polymers, the thin films are preferably tuned to promote balanced
electron and hole transport between the first and second
electrodes. Typical organic electronic devices include, but are not
limited to, a LED, a thin film transistor, a photovoltaic solar
cell, an electrochemical luminescent display device, an
electrochromic display device, and an electroluminescent device for
active flat-panel display applications.
[0032] FIG. 1 shows the sectional structure of a typical single
layer light-emitting device 10. The LED device 10 includes a clear
substrate 12 having an anode coating 14. A single layer of
deuterated semiconducting luminescent polymer 16 is deposited
between the anode 14 and a cathode 18. An electrical potential 20
connects the anode 14 and cathode 18.
[0033] In many cases, a double or a multi-layer LED may be
fabricated, in which one or two different charge-transporting
layers are used. The charge-transporting layer may be an
electron-transporting layer or a hole-transporting layer. Each
individual layer may be a polymeric or organic film with a
thickness less than 1500 nm, preferably less than 300 nm.
[0034] FIG. 2 shows a section diagram of a typical three-layer LED
30. As shown in FIG. 2, the anode substrate 34, preferably ITO on a
clear substrate 32, may be pre-coated with a layer of a
hole-transporting material 36 either by spin-coating, or by
printing. A typical hole-transporting layer 36 can be selected
from, but not limited to, polyaniline, poly(phenylenevinylene),
poly(3,4-ethylenedioxy-thiophene) (PEDOT) (doped with polystyrene
sulfonic acid), poly(N-vinyl carbazole) (PVK), or an aromatic amine
organic compound or polymer. The thickness of the hole-transporting
layer 36 is preferably between 0.5 nm to 500 nm, and more
preferably less than 150 nm. A deuterated semiconducting
luminescent polymer layer 38 is disposed on the hole-transporting
material 36. The solvent used to fabricate the luminescent polymer
layer 38 is selected to be compatible hole-transporting layer 36
such that it does not dissolve the hole-transporting layer 36.
Depending on the luminescent polymer utilized, the luminescent
layer 38 can emit various colors from red, yellow, green, to blue.
The thickness of the luminescent layer 38 is preferably between 10
nm to 300 nm, preferably between 50 nm to 200 nm.
[0035] The device 30 may be further coated with a layer of an
electron-transporting material 40 either by spin-coating or by
printing. A typical electron-transporting layer 46 can be selected
from, but is not limited to, poly(aromatic oxadiazole) [X. -C. Li,
et al., J. Chem. Soc. Chem. Commun., p. 2211, 1995], organic
compounds containing aromatic oxadiazoles, triazoles, quinolines,
such as 2-tert-butyl-phenyl-5-bipheny- l-1,3,4-oxadiazole (PBD),
and Alq3. Evaporation or solution coating may be employed. For
solution coating (spin-coating or printing), it is again important
to select a suitable solvent for the electron transporting solution
or ink that does not corrode or dissolve the luminescent polymer
layer 38, hole-transporting layer 44, or anode 42. Luminescent
polymers formulated as luminescent ink with cross-linking ability
may be used. In a preferred embodiment, the cross-linking process
can be accomplished by UV irradiation or moderate thermal treatment
(less than 300.degree. C.) of the inked anode substrate after
printing.
[0036] The cathode metal 42 can be deposited either by thermal
vacuum evaporation, or by sputtering. The presently preferred
cathode metals are aluminum, calcium and magnesium. The thickness
of the cathode layer 42 is preferably between 0.5 nm to 5000 nm,
preferably thicker than 50 nm. An electrical potential 44 connects
the anode 34 and cathode 42.
EXAMPLES
[0037] The following examples are given to illustrate various
embodiments within the scope of the present invention. These are
given by way of example only, and it is to be understood that the
following examples are not comprehensive or exhaustive of the many
types of embodiments of the present invention that can be prepared
in accordance with the present invention.
Example 1
[0038] Green Luminescent Poly(Phenylene Vinylene) With Deuterium
via Bromo-Precursor Route: 9
[0039] Synthesis of deuterated 1,4-bisbromomethyl-benzene 2:
Deuterated Xylene-d10 (1.644 g, 14.14 mmol) and N-bromosuccinimide
(NBS) (5.6 g, 28.99 mmol) were dissolved in carbon tetrachloride
(15 mL) at room temperature. After being degassed 3 times, the
mixture was heated by an IR lamp to reflux using light irradiation.
The reaction was carried out for 6 hours, and cooled down to room
temperature. After filtration, the solid was washed by
dichloromethane (3.times.30 mL), and the solution portions were
collected. Evaporation of the solvents gave oil product that was
purified by silica flash column using hexane and the mixture of
ethyl acetate/hexane (1:10, v/v) to give white solid 2 (1.87 g,
49%). Rf=0.46 (EtOA/hexane, 1:3, v/v).
[0040] Synthesis of bromo-precursor deuterated PPV 3: Deuterated
1,4-bisbromomethyl-benzene 2 (0.8 g, 2.941 mmol) was dissolved in
anhydrous tetrahydrofuran (7 mL) and degassed. The solution was
cooled down to 0.degree. C. using an ice bath. Potassium
tert-butoxide (2.94 mL, 1.0 M in THF, 2.94 mmol) was added into the
solution dropwise. The addition was finished within 20 minutes, and
the light yellow solution was stirred at 0.degree. C. for 4 hours.
The solution was poured into methanol (100 mL) to give the
precursor polymer precipitate (58%).
[0041] Luminescent thin film of deuterated PPV 4 via
bromo-precursor 3: The yellow polymer 3 can be soluble in THF, and
a thin polymer film of 3 can be cast on a glass substrate. Green
luminescent polymer 4 can be obtained by heat treatment of 3 at
160.degree. C. for 4 hours under nitrogen or under vacuum.
Examples 2
[0042] Green Luminescent Poly(Phenylene Vinylene) With Deuterium
Substituents Via Sulfonium-Precursor Route: 10
[0043] Synthesis of sulfonium monomer 5: Deuterated
1,4-bisbromomethyl-benzene 2 (1.0 g, 3.676 mmol) and
tetrahydrothiophene (1.62 g, 18.5 mmol) were dissolved in anhydrous
methanol (12 mL), and the mixture was heated to 50.degree. C. The
reaction was carried out under nitrogen for 16 hours. The solvent
was evaporated under vacuum to give white slurry that was washed by
anhydrous chloroform (1.times.8 mL). The beige powder was dried
under vacuum at 0.degree. C. to yield the sulfonium monomer 5 (1.2
g, 68%).
[0044] Synthesis of sulfonium-precursor deuterated PPV 6: The
sulfonium monomer 5 (1.1 g, 2.30 mmol) was dissolved in methanol (8
mL) at 0.degree. C. The mixture was degassed before the addition of
sodium hydroxide (5.6 mL, 0.4 N in water, 2.25 mmol). The addition
of NaOH was finished within 15 min. After reaction at 0.degree. C.
for 2 hours, the colorless solution was dialyzed against degassed
water using a dialysis tube (Lancaster) to remove oligomers and
inorganic species. The dialysis process was repeated for 2 more
times, with final dialysis against methanol. The resulting polymer
6 has a yield of 60%, and it is ready to prepare polymer thin
films.
[0045] Luminescent thin film of deuterated PPV 7 via
sulfonium-precursor 6: The sulfonium polymer 6 is soluble in water
and methanol, and is stable at 0.degree. C. Polymer 6 is normally
obtained in the mixture solvent of methanol and water with a
concentration of 1% which is ready to cast thin film on glass
substrate. Green luminescent polymer 7 can be obtained by heat
treatment of 6 at 160.degree. C. for 4 hours under nitrogen or
under vacuum.
[0046] When the polymer 6 is converted to 7, its conjugation length
is increased which is shown in the UV-Visible spectroscopy. FIG. 3
shows the UV spectral change of this conversion, showing the band
gap changes from 3.42 eV to 2.45 eV. After conversion, the polymer
7 fluoresces green with the PL peak located at 550 nm, shown in
FIG. 4.
Example 3
[0047] Normal PPV Polymer Synthesis Via Sulfonium Precursor (for
Comparison).
[0048] Normal PPV precursor polymer can be obtained by
polymerization of the monomer, (Aldrich) following the similar
procedure as illustrated in example 2. The normal PPV polymer has
very similar optical and electronic properties as D-PPV.
Comparative photoluminescence (PL) quantum efficiency measurements
showed that the deuterated PPV photoluminescence quantum efficiency
compared to that of normal PPV was: DPPV/PPV=1.2, which means that
the deuterated PPV has a brighter photoluminescence than normal
PPV.
Example 4
[0049] Red Luminescent Partially Deuterated
Poly(2-methoxy-5-ethylhexyloxy- -phenylene Vinylene) (Partially
Deuterated MEH-PPV). 11
[0050] The synthesis of phenylene
1-(2-ethyl-hexyloxy)-4-methoxy-benzene 9: 4-methoxylphenol (24.8 g,
200 mmol) and sodium hydroxide pellets (8.8 g, 220.0 mmol) were
charged into a 500 mL two neck flask equipped with a condenser and
a septum. The flask was degassed 3 times before adding anhydrous
methanol (150 mL) via an annular tube. The solution became hot
while stirring. It was heated to reflux for 20 min, and then cooled
down to room temperature. 2-Ethyl-hexyl bromide (39 mL, 220 mmol)
was then added by a syringe at room temperature, dropwise (15
min.). The mixture was heated to reflux for 20 hour. The methanol
was removed by distillation, and then 150 mL ether was added.
Deionized water (100 mL) was added to dissolve inorganic salts. The
aqueous phase was washed by ether (3.times.50 mL), and the combined
portions of ether was washed by brine (2.times.50 mL), dried over
sodium sulfate, and evaporated to remove ether. The obtained oil
was fraction distillated to remove the unreacted ethylhexyl
bromide, and the final product was collected in the fraction of
130-135.degree. C. (2 mm Hg) as a clear oil (35.8 g, 76%).
[0051] Synthesis of
1,4-bis-chloromethyl-d4-2-(2-ethylhexyloxy)-5-methoxy-- benzene 10:
1-(2-ethyl-hexyloxy)-4-methoxy-benzene 9 (5.9 g, 24.97 mmol) and
parafoadehyde-d2 were charged into a 100 mL two neck flask, and
degassed by pumping/nitrogen inlet (3 times). Hydrochloric acid
(37%, 11.2 mL, 500 mmol) was added by a syringe. While stirring at
room temperature, acetic anhydrate was added dropwise to control
keep the reaction mixture from becoming too hot. The addition of
the acetic anhydrate was finished within 30 minutes. The mixture
was then heated to 75.degree. C. under nitrogen while stirring.
After reaction of 8 hours, the mixture was poured into water (200
mL), and the aqueous phase was extracted with ethyl acetate
(3.times.80 mL). The combined organic phase was washed with brine
(2.times.50 mL), dried over magnesium sulfate. Evaporation of the
organic solvent yielded the crude slurry, which was purified by a
silica flash column using hexane and ethyl acetate/hexane mixture
(10% to 20%) to give the product (45%). Rf=0.66 (EtOAC/hexane, 1/3,
v/v).
[0052] Synthesis of poly(2-methoxy-5-ethylhexyloxy-phenylene
vinylene) with deuterium substituent on vinyl (partially deuterated
MEH-PPV) 11: 1,4-bis-chloromethyl-d4-2-(2-5-methoxy-benzene 10
(0.62 g, 1.84 mmol) was charged into a 100 mL two neck flask and
degassed by pumping/nitrogen inlet (3 times). Anhydrous
tetrahydrofuran (60 mL) was added to dissolve the monomer.
Potassium tert-butoxide solution (11.0 mL, 1.0 M in THF, 11.0 mmol)
was added dropwise into the stirring solution within 20 min. The
colorless solution became red and viscous. The reaction was carried
out under nitrogen for 18 hours under dark condition. The viscous
solution was poured into methanol (300 mL) to give a red
precipitate, which was purified by repeated precipitation (2 times
more) from its solution of chloroform into methanol. A red polymer
was obtained with a yield of 56%.
[0053] The partially deuterated MEH-PPV had a .pi.-.pi.* band gap
of 2.1 eV as illustrated in FIG. 5. The polymer luminesces red in
solution and in thin film states. FIG. 5 shows the photoluminescent
spectrum (excited by 400 nm UV light), showing a red luminescent
color (located around 620 nm).
Example 5
[0054] Red Luminescent MEH-PPV With Deuterium Atom Substituents on
Both Vinyl and on Phenyl: 12
[0055] According to the above synthesis scheme, the red luminescent
deuterated MEH-PPV 15 is prepared following the similar chemical
procedure as described in Example 4. The compound 13 is prepared by
the chemistry procedure described in: H. Tsuzuki, et al., J. Chem.
Research, 1994, 1701-1716.
Example 6
[0056] Red Luminescent Poly(2,5-dioctyl-phendylene Vinylene) With
Deuterium Atom Substituents on Vinyl and on Phenyl: 13
[0057] By using the deuterated starting compound 16, red
luminescent poly(dioctylocyl-phenylene vinylene) 19 can be prepared
according to the above scheme with the similar procedures as
described in Example 4.
Example 7
[0058] Blue Luminescent Poly(9,9'-dioctyl-fluorene) With Deuterium
Atom Substituents. 14
[0059] By using the deuterated fluorene 20, blue luminescent
poly(9,9-dialkyl fluorene) 23 can be prepared according to the
above scheme with the similar procedures as described in E. P. Woo
et al., U.S. Pat. No. 5,962,631.
Example 8
[0060] Phosphorescent Dopant Metal Complex With Deuterium Atoms.
15
[0061] By using the deuterated compound 24, phosphorescent dopant
metal complex 28, fac-tris(2-phenylpyridine)iridium Ir(ppy)3), was
prepared according to the above scheme with the similar procedures
and application mechanism as described in [M. D. McGehee, et al.,
Adv. Mater. 1999, 11(16), 1349; Appl. Phys. Lett., 1999, 75,
4].
[0062] D-9-2-Phenylpyridine 26 was synthesized according to Organic
Syntheses Vol. 2, p. 517. The yield of the compound was 21%.
D-24-lr(ppy)3 28 was synthesized according to Inorganic Chemistry,
1991, 30(8), 1685. The yield of this compound was 19%. These
compounds were confirmed by 1H-NMR, which showed no signals due to
protons. Parent peak, 164, of D-9-2-phenylpyridine was observed in
MS spectrum, and also D-24-Ir(ppy)3 showed 678.7 as the parent
peak.
Example 9
[0063] Deuterated Alq3: Green Luminescent Compound Preparation.
16
[0064] By using the deuterated quinoline 29, green luminescent
metal complex 35, deuterated tris-(8-hydroxyquinoline) aluminum,
can be prepared according to the above scheme with the similar
procedures and application mechanism as described in: [Kuznetsoua,
"Complex compounds of metals with some nitrogen containing
ligands", Zhurnal obshchey khimii, vol. XLVI (CVIII), No. 3, March
1976, pp. 670-675; Hamada et al., "Organic Electroluminescent
Devices with 8-Hydroxyquinoline Derivative-Metal Complexes as an
Emitter," Japanese Journal of Applied Physics, vol. 32, Part 2, No.
4A, Apr. 1, 1993, pp. L514-L515; Tang et al., "Organic
electroluminescent diodes," Applied Physics Letters, vol. 51, No.
12, Sep. 21, 1987, pp. 913-915.]
Example 10
[0065] Electroluminescence of Fac-Tris(2-Phenylpyridine)iridium
Ir(ppy).sub.3 (For Comparison).
[0066] A device of ITO/NPD 40 nm/CBP+11% Ir(ppy).sub.3 20 nm/BCP 10
nm/Alq3 40 nm/LiF 0.75 nm/Al, where NPD denotes to
N,N'-bis(naphthyl)-N,N'-diphenylbenzidine, CBP denotes to carbazole
biphenyl, was fabricated following a similar procedure as described
in: Appl. Phys. Lett., 75, 4 (1999). Each layer was formed and
controlled by vacuum thermal evaporation. The NPD was used as a
hole transporting layer; the CBP was used as the host with the
phosphorescent dopant, Ir(ppy).sub.3, as the emissive layer; BCP
was used as the exciton blocking layer; Alq3 as electron
transporting layer; LiF was used as cathode modification layer; Al
was used as the cathode metal. Bright green luminescence
(electrophos-phorescence) was observed at a voltage of 5 V. The
electroluminescence spectrum was shown in FIG. 6.
Example 11
[0067] Electroluminescence of Fac-Tris(2-Phenylpyridine)iridium-d8
Ir(ppY).sub.3-d8.
[0068] A device of ITO/NPD/CBP+11% Ir(ppy).sub.3-d8 20 nm/BCP 10
nm/Alq3 40 nm/LiF 0.75 nm/Al, was fabricated following a similar
procedure as described in Example 10. Bright green luminescence
(electrophosphorescence) was observed at a voltage of 5 V. The
electroluminescence spectrum was shown in FIG. 7.
[0069] FIG. 8 shows the relationship of quantum efficiency (%,
photons per electron) vs. current density (mA/cm.sup.2) for the
device in Example 10 (square symbols) with the device of Example 11
using deuterium Ir(ppy)3-d8 (circle symbols). From FIG. 8, the
device of Example 11 has higher quantum efficiency than the device
of Example 10.
[0070] FIG. 9 shows the relationship of luminance efficiency (1
m/W) vs. current density (mA/cm.sup.2) for the device in Example 10
(square symbols) with the device of Example 11 using deuterium
Ir(ppy)3-d8 (circle symbols). From FIG. 9, the device of Example 11
has higher luminance efficiency than the device of Example 10.
[0071] It will be appreciated that the present invention provides
new organic semiconductor materials that exhibit high luminescence,
excellent stability, and good lifetime. This is achieved by
chemically modifying known and novel optoelectronic materials by
replacing protons with deuterium atoms on the conjugated
chromophores. New luminescent organic materials are designed and
synthesized containing deuterium atoms for their application in
optoelectronic devices, including light-emitting devices. Such
OLEDs prepared with deuterated organic semiconductor materials have
brighter luminance and better thermal stability compared to
non-deuterated organic semiconductor materials.
[0072] The present invention may be embodied in other specific
forms without departing from its essential characteristics. The
described embodiments are to be considered in all respects only as
illustrative and not restrictive. The scope of the invention is,
therefore, indicated by the appended claims rather than by the
foregoing description.
* * * * *